Glycolate ester peracid precursors

ABSTRACT

The invention provides novel bleaching compositions comprising peracid precursors with the general structure   &lt;IMAGE&gt;   with R, R&#39;, R&#39;&#39; and L as defined in the specification. Novel peracids and precursors are also herein disclosed. These peracid precursors provide new, proficient and cost-effective compounds for fabric bleaching.

a division of U.S. Ser. No. 06/928,070, filed Nov. 6, 1986, now U.S.Pat. No. 4,778,618.

BACKGROUND OF THE INVENTION

1. Field of the Invention

This invention relates to a new class of chemical compounds andcompositions useful in providing efficient bleaching of textiles over awide range of washing temperatures, but especially at low temperatures(less than about 50° C.). The present invention provides a new compoundfor use in detergent bleaches or as laundry additives, said compoundhaving the general formula ##STR2## wherein R is C₁₋₂₀ linear orbranched alkyl, alkylethoxylated, cycloalkyl, aryl, substituted aryl: R'and R" are independently H, C₁₋₂₀ alkyl, aryl, C₁₋₂₀ alkylaryl,substituted aryl, and NR₃ ^(a+), wherein R^(a) is C₁₋₃₀ alkyl; and L isessentially any useful leaving group which can be displaced in aperoxygen bleaching solution by perhydroxide anion. It is most preferredthat R' and R" are both H, and thus R'--C--R" is methylene. The alphahydroxy substituted carbon plus the carbonyl form the glycolate group.When the precursor is combined with a source of hydrogen peroxide, thisreaction results in the formation of a peracid, and, under certaincircumstances, uniquely to this invention, in the formation of a mixtureof peracids. The structure and reactivity of the compounds are unique inthat higher yields of peracids can be obtained across a broader pH rangeand temperature than conventional fatty acid based bleach activators.

2 Brief Description of the Prior Art

Numerous substances have been disclosed in the art as effective bleachactivators. British Patent Specification No. 1,147,871, Boldingh et al,describes bleaching and detergent compositions containing an inorganicpersalt and acyloxyalkyl or acyl benzene sulfonates. It is claimed thatsuch esters provide improved bleaching temperatures below 70° C. whencompared to compositions using the persalt alone.

These activators are represented by the formula: ##STR3## whereinX=branched or straight chain alkyl or acyl radical containing 6-17carbon atoms; R=H or alkyl radical having 1--7 carbon atoms; and M=analkali metal, or ammonium radical.

Chung et. al., U.S. Pat. No. 4,412,934, discloses bleaching compositionscontaining a peroxygen bleaching compound and a bleach activator of thegeneral formula ##STR4##

wherein R is an alkyl group containing from about 5 to about 18 carbonatoms; L is a leaving group, the conjugate acid of which has a pK_(a) inthe range of about 6 to about 13. Chung et al focuses on alkanoyloxybenzene sulfonates, which have been previously disclosed in G.B. No.864,798, Hampson et al.

Thompson et. al. U.S. Pat. No. 4,483,778, discloses bleach activators ofthe structure ##STR5## wherein R is C₄₋₁₄ alkyl, R.sup. is H or C₁₋₃alkyl, X is --C1. --OCH₃, or --OCH₂ CH₃, and L is a leaving group whoseconjugate acid has a pK_(a) of 4-30. Unlike the apparently crowded alphacarbon in the Thompson et al compound, the present invention hasnon-hindered enhanced perhydrolytic reactivity. EP No. 166 571, Hardyet. al, discloses the use of a bleach activator compound of the formula[RX]_(m) Al, wherein R is hydrocarbyl. C₆₋₂₀ alkylsubstituted aryl, oralkoxylated hydrocarbyl; X is O, SO₂, N(R¹)₂, (R¹)P→O or (R¹)N→O,wherein for m=1, A includes ##STR6## oxybenzene sulfonate.

E.P. 170 368, Burns et al, discloses the use of amide esters of theformula ##STR7## wherein R¹ and R² are alkyl(ene) aryl(ene) oralkylaryl(ene) with 1-14 carbon atoms and R⁵ is H, an alkyl,

or alkylaryl group with 1-10 carbon atoms.

SUMMARY OF THE INVENTION

The present invention provides, in one embodiment, a perhydrolysissystem comprising:

(a) a bleaching effective amount of a peracid precursor compound havingthe general structure ##STR8## wherein R is C₁ --C₂₀ linear or branchedalkyl, alkylethoxylated. cycloalkyl, aryl, substituted aryl; R' and R"are independently H, C₁₋₂₀ alkyl, aryl, C₁₋₂₀ alkylaryl; substitutedaryl, and NR₃ ^(a+), wherein R^(a) is C₁₋₃₀ ; and L is essentially anyuseful leaving group which can be displaced in a peroxygen bleachingsolution by perhydroxide anion; and

(b) a bleach effective amount of a compound which provides hydrogenperoxide in aqueous media.

The invention further provides a novel peracid having the structure##STR9## wherein R, R', and R" are as defined above.

The invention also provides novel peracid precursors having thestructure ##STR10## in which L is selected from the group consistingessentially of: phenol derivatives; oxynitrogen groups (amine oxide,hydroxyimide and oxime groups); and carboxylic acids (from mixedesters).

In a further embodiment, the invention provides a bleaching compositioncomprising:

(a) a bleach effective amount of a compound including the substituent##STR11## (b) a bleach effective amount of a source of hydrogen peroxide

DETAILED DESCRIPTION OF THE INVENTION

The present invention provides new compounds and compositions useful forlow temperature fabric bleaching applications. The compounds of interestto the invention, ##STR12## wherein each substituent is as hereinbeforedefined, provide several advantages over previously disclosedcompositions, for example:

1. Superior Low Temperature Reactivity: Many peracid precursors sufferfrom low rates of reaction and require exceedingly high temperatures toprovide effective bleach. Exemplary of such activators aretetracetylglycouril (TAGU) and tetraacetyl ethylene diamine (TAED). Theprecursors of the invention provide effective bleaching at the lowtemperatures prevalent in U.S. washing conditions (generally, under 100°F.).

2. Higher peracid yields Across a Wider pH Range: Prior peracidprecursors have been limited by the fact that pH of wash liquors whichare optimal for fabric laundering or bleaching may be inimical to insitu formation of peracids, and vice versa. The present invention is notas affected by this phenomenom.

3. Provides Mixture of Peracids Under Selected Conditions: Depending onthe reaction conditions, the precursors of the present invention canbeneficially provide more than one type of peracid. At pH 10.5 orgreater, hydroperoxide anion is believed to combine with the precursorsto form at least two different peracids. As an example, if the inventiveprecursor is octanoyl glycolate. ##STR13## formation of up to threedifferent peracids, may occur: ##STR14##

The first and third peracids produced, alkanoyloxyperacetic acid andperglycolic acid, are new bleaching compounds.

4. Effectiveness Not Substantially Tied to Molar Ratio of H₂ O₂Precursor: In Chung et al, U.S. Pat. No. 4,412,934, it has been allegedthat the amount of hydrogen peroxide must exceed the precursor in amolar excess in order to achieve meaningful amounts of peracid. However,the present invention is not so restricted.

The invention also allows the use of less amenable leaving groupspreviously not possible with conventional fatty acid based esters forhydrogen peroxide activation purposes. The enhanced reactivity of thenovel compounds is the result of structural modifications to the acylgroup to reduce the pKa of the corresponding carboxylic acid. The changein reactivity has been accomplished via attachment of a moreelectronegative atom, X, or an electron withdrawing group, ##STR15## inthe structure ##STR16## at the alpha-position to the terminal carbonylgroup. In the present invention, X=oxygen, and relates to acylglycolicacid esters and derivatives thereof. X, however, could also be anotherelectronegative atom, such as --S--(sulfide).

The base carbonyl is a glycolic acid derivative. The glycolic acidderivatives have been found surprisingly effective in this invention.

Most preferably, when the heteroatom, X is oxygen, and the carbylenegroup is methylene (R' and R" are both H), the effect of anelectronegative substituent alpha to the terminal carbonyl enhances thereactivity of the inventive precursors.

The electronic effect of this modification at the proximal methylenegroup appears to make the carbonyl group more susceptible tonucleophilic attack by a perhydroxide anion. The resulting enhancedreactivity results in higher peracid yields at low temperatures (e.g.,70° F.), across a broader pH range, and makes the perhydrolysis reactionto generate peracids less susceptible to critical activator to H₂ O₂ratios. The following tables illustrate these points:

                  TABLE I                                                         ______________________________________                                        A. MOLAR RATIO EFFECT                                                                             Molar.sup.3                                                                           % Peracid                                                   Temp.     Ratio   Yield, pH 9.5                                     ______________________________________                                        C8-NOBS.sup.1                                                                             70°  2/1     45                                                        70°  1/1     35                                            C8-Glycolate.sup.2                                                                        70°  2/1     85                                                        70°  1/1     80                                            ______________________________________                                         .sup.1 Octanoyloxybenzene sulfonate, peracid activator as described in        U.S. Pat. No. 4,412,934.                                                      .sup.2 Octanoyl glycolate (invention)                                         .sup.3 molar ratio of H.sub.2 O.sub.2 : precursor/activator              

                  TABLE II                                                        ______________________________________                                        B. pH EFFECT                                                                                            % Peracid                                                             Molar.sup.3                                                                           Yield, pH                                                     Temp.   Ratio   10.5     9.5 8.5                                    ______________________________________                                        C8-NOBS.sup.1                                                                             70°                                                                              2/1     79     45  11                                   C8-Glycolate.sup.2                                                                        70°                                                                              2/1     90     85  63                                   ______________________________________                                         .sup.1 Octanoyloxybenzene sulfonate, peracid activator as described in        U.S. Pat. No. 4,412,934.                                                      .sup.2 Octanoyl glycolate (invention)                                         .sup.3 molar ratio of H.sub.2 O.sub.2 : precursor/activator              

                  TABLE III                                                       ______________________________________                                        C. TEMPERATURE EFFECT                                                                             Molar.sup.3                                                                           % Peracid                                                   Temp.     Ratio   Yield, pH 9.5                                     ______________________________________                                        C8-NOBS.sup.1                                                                              70° 2/1     45                                                        100° 2/1     44                                            C8-Glycolate.sup.2                                                                         70° 2/1     85                                                        100° 2/1     93                                            ______________________________________                                         .sup.1 Octanoyloxybenzene sulfonate, peracid activator as described in        U.S. Pat. No. 4,412,934.                                                      .sup.2 Octanoyl glycolate (invention)                                         .sup.3 molar ratio of H.sub.2 O.sub.2 : precursor/activator              

The preferred precursors of the invention are derivatives of glycolicacid, also known as hydroxyacetic acid. Thus, the inventive precursorsmay be also designated as acyloxyacetic acid esters. A novel chemicalproperty of these acyloxyacetic acid esters is that uniquely at pH's ofabout 10.5 or higher, as many as three different peracids (I-III, seeabove, page 5) can be generated. This is advantageous because it wouldallow bleaching of a wider range of stains.

However, unique to this invention, the subject compounds have addedflexibility in that if only the acyloxyperacid is desired for aparticular application, this can be achieved by maintaining a H₂ O₂/ester molar ratio of about 1.0, or by lowering the pH to <10. Thisflexibility is not available to prior art disclosures, including theacyl amidoacetic esters disclosed in EP No. 170386.

It has been surprisingly found that the second perhydrolysis is highlydependent on the structure of the terminal carbonyl moiety ##STR17##

If R¹ 32 H (i.e., acylglycolic acid), no secondary perhydrolysis occurs.

If R¹ =OH (i.e, alkanoyloxyperacetic or acylperglycolic acid), secondaryperhydrolysis occurs and a mixture of peracids is obtained. ##STR18##(i.e., acyl glycolic acid, p-phenyl sulfonate ester), the firstperhydrolysis occurs at the terminal carbonyl moiety to form thealkanoyloxyperacetic acid, which at pH greater than 10.0 undergoes thesecondary perhydrolysis to generate the mixture of peracids.

The advantages of this chemistry is that at pH 10.5, it is feasible todeliver three different peracids (I-III) with differing levels ofhydrophilicity and hydrophobicity. It is believed that this mixture ofperacids would allow bleaching across a wider range of stains than thatpossible with conventional bleaching activators.

The enhanced reactivity of the inventive compounds also affords someunique advantages for their use in bleaching compositions. The prior art(Chung, et. al., U.S. Pat. No. 4,412,934,) discloses that specific molarratios of hydrogen peroxide to bleach activator of greater than about1.5, preferably 2.0, are critical to obtaining the desired level ofperacid needed for effective bleaching. The criticality of the molarratio was ascribed to a hydrophobic-hydrophobic interaction of the alkylchain of the acyl group of the peracid and the unreacted activator,which results in formation of diacylperoxides and limits peracid yields.Chung et al, U.S. Pat. No. 4,412,934, stipulates that ratios higher than1.5 of H₂ O₂ to activator reduce this problem. The contended novelty ofChung et al's invention is that the enhanced reactivity of the subjectcompounds allows high peracid yields at molar ratios of H₂ O₂ toactivator of greater than about 1.5.

In the present invention, the non-binding theory is proposed that theelectron withdrawing effects of an alpha-substituent make the terminalcarbonyl carbon more susceptible to nucleophilic attack by OOH⁻, andthus excess OOH⁻ is not required to drive the perhydrolysis reaction tocompletion. Additionally, it is proposed that by introducing an esterfunctionality in close proximity to the terminal carbonyl group,sterically or via polarization effects the hydrophobic-hydrophobicinteraction is minimized which appears to be responsible fordiacylperoxide formation.

Prior art disclosures (Thompon Et. Al. U.S. Pat. No. 4,483,781,) revealthat alpha-chloro and alpha alkoxy esters are contended to be useful asperhydrolysis precursors. The acyloxyacetate esters of the invention, onthe other hand, have inherent advantages in that the terminal carbonylis sterically less crowded and have unique properties which allowdelivery of mixtures of peracids.

An additional advantage of this invention is that the second esterfunctionality significantly modifies the odor of the resulting peracidor carboxylic acid formed. The malodor associated with fatty acid basedperacids is well known. The acyloxyacetic acid esters provide aneffective solution to the odor problem. However, if it is desirable toexecute this chemistry at pH>10, the generation of a mixture of peracidswould result in lower odor because of the higher solubility of the insitu generated peracids in highly alkaline media.

The uniqueness of the proposed invention is that the enhancedperhydrolysis reactivity of the subject compounds compared to the fattyacid based esters may allow the use of less amenable leaving groups inthe precursor such as hydroxyimides or oxime, and related oxynitrogengroups. Such leaving groups would be impractically slow forperhydrolysis purposes on fatty acid based esters.

In summary, the compounds of the present invention, especially theacyloxyacetic acid esters. Possess significant advantages in reactivity.yields, and bleaching performance over the fatty acid based esterprecursors. They generate much less of the malodor associated with fattyperacids, they function over a broader pH range and at low temperatures.At pH greater than 10 and H₂ O₂ /activator molar ratios greater than 1,a mixture of peracids can be obtained. They do not require a criticalmolar ratio of H₂ O₂ to activator, and the mixture of peracids formed atpH greater than 10 allow bleaching over a wider range of stains.

The general structure of the invention is ##STR19## with R, R', R" and Las previously defined.

In one embodiment of the invention is provided:

A bleaching composition comprising:

(a) a peracid precursor having the general structure: ##STR20## whereinR is C₁₋₂₀ linear or branched alkyl, alkoxylated alkyl, cycloalkyl,aryl, alkylaryl, substituted aryl; R' and R" are independently H, C₁₋₂₀alkyl, aryl, C₁₋₂₀ alkylaryl, substituted aryl, and NR₃ ^(a+), whereinR^(a) is C alkyl; and L is a leaving group; and

(b) a bleach-effective amount of a source of hydrogen peroxide.

In the following discussion, certain definitions are utilized:

Peracid precursor is equivalent to bleach activator. Both termsgenerally relate herein to reactive esters which have a leaving groupsubstituent, which during perhydrolysis, actually cleave off the acylportion of the ester.

Perhydrolysis is the reaction which occurs when a peracid precursor oractivator is combined in a reaction medium (aqueous medium) with aneffective amount of a source of hydrogen peroxide.

The leaving group is basically a substituent which is attached via anoxygen bond to the acyl portion of the ester and which can be replacedby a perhydroxide anion (OOH--) during perhydrolysis. The basic reactionis: ##STR21## Although further discussion below will elaborate on theunique advantages of the preferred embodiment, ##STR22## also referredto as a glycolate ester or as an acyloxyglycolate ester, at present, theconstituent portions of the ester. i.e., the acyl group and the leavinggroups are herein defined.

R is defined as being C₁₋₂₀ linear or branched alkyl, alkoxylated alkyl,cycloalkyl, aryl, substituted aryl or alkylaryl.

It is preferred that R is C₁₋₂₀ alkyl or alkoxylated alkyl. Morepreferably, R is C₁₋₁₀, and mixtures thereof. R can also bemono-unsaturated or polyunsaturated. If alkoxylated, ethoxy (EO)--(--OCH₂ CH₂) and propoxy (PO) --(--OCH₂ CH₂ CH₂) groups are preferred,and can be present, per mole of ester, from 1-30 EO or PO groups, andmixtures thereof.

It is especially described for R to be from 4 to 17, most preferably 6to 12, carbons in the alkyl chain. Such alkyl groups would be surfaceactive and would be desirable when the precursor is used to form surfaceactive peracids for oxidizing fat or oil based soils from substrates atrelatively low temperatures.

It is further highly preferred for R to be aryl and C₁₋₂₀ alkylaryl. Adifferent type of bleaching compound results when aromatic groups areintroduced onto the ester.

Alkyl groups are generally introduced onto the ester via an acidchloride synthesis discussed further below. Fatty acid chlorides such ashexanoyl chloride, heptanoyl chloride, octanoyl chloride, nonanoylchloride, decanoyl chloride and the like provide this alkyl moiety.Aromatic groups can be introduced via aromatic acid chlorides (e.g.,benzoyl chloride) or aromatic anhydrides (e.g., benzoic acid anhydride).

R' and R" are independently H, C₁₋₂₀ alkyl, aryl, C₁₋₂₀ alkylaryl,substituted aryl, and NR₃ ^(a+), wherein R^(a) is C₁₋₃₀ alkyl. When R'and R" are both alkyl, aryl, alkylaryl, substituted alkyl, or mixturesthereof, preferably the total number of carbons of R' +R" does notexceed about 20, more preferably does not- exceed about 18: Alkyl ofabout 1-4 are preferred. If R' or R" are substituted aryl, substituentsinclude OH⁻, SO₃ ⁻, and CO₂ ⁻ ; R' or R" can be NR₃ ^(a+) (R^(a) isC₁₋₃₀ carbons, and preferably, two of R^(a) are short chain (C₁₋₄)alkyls and one of R^(a) is a long chain alkyl (C₆₋₂₄) Appropriatepositive counterions to include Na+, K⁺, etc. and appropriate negativecounterions include halogen (e.g., C.sup.⁻), OH⁻ and methosulfate. It ispreferred that at least one of R' and R" be H, and most preferably, both(thus forming methylene).

Although applicants have briefly mentioned the importance of the R' andR" alpha, alpha substituents on the carbylene of the acyl group, it isagain stressed that the position of various substituents alpha to theproximal carbonyl is very important to this invention.

The leaving group, as discussed above, is basically capable of beingdisplaced by perhydroxide anion in aqueous medium. Unlike prior artprecursors, the invention is not limited to leaving groups havingparticular solubility or reactivity criteria due to the reactiveness ofthe acyl of the inventive precursor.

Thus, the preferred leaving groups, none of which are meant to limit theinvention, include:

(a) phenol derivatives

(b) halides

(c) oxynitrogen leaving groups

(d) carboxylic acid (from a mixed anhydride)

(a) Phenol Derivatives

The phenol derivatives can be generically defined as: ##STR23## whereinY and Z are, individually H. SO₃ M. CO₂ M, SO₄ M, OH, halo substituent,--OR², R³, NR₃ ⁴ X, and mixtures thereof, wherein M is an alkali metalor alkaline earth counterion, R² of the OR² substituent is C₁₋₂₀ alkyl,R³ is C₁₋₆ alkyl, R⁴ of the NR₃ ⁴ substituent is C₁₋₃₀ alkyl, X is acounterion, and Y and Z can be the same or different.

The alkali metal counterions to sulfonate, sulfate or carbonate (all ofwhich are solubilizing groups) include K⁺, Li⁺ and most preferably, Na+.The alkaline earth counterions include Sr⁺⁺, Ca⁺⁺, and most preferably,Mg⁺⁺. Ammonium (NH₄ ⁺) and other positively charged counterionssuitable. The halo substituent can be F, Br or most preferably, C₁. When--OR², alkoxy, is the substituent on the phenyl ring. R² is C₁₋₂₀, andthe criteria defined for R on the acyl group apply. When R³ is thesubstituent on the phenyl ring, it is a C₁₋₁₀ alkyl, with preferencegiven to methyl, ethyl, N- and isopropyl. N-, sec- and tertbutyl, whichis especially preferred.

When --NR₃ ⁴ X, quaternary ammonium, is the substituent, it is preferredthat two of R⁴ be short chain alkyls (C₁₋₄, most preferably, methyl) andone of the R⁴ alkyls be longer chain alkyl (e.g., C₈₋₃₀), with X, anegative counterion, preferably selected from halogen (Cl⁻, F^(`), Br⁻,I⁻), CH₃ SO₄ ⁻ (methosulfate), NO₃ ⁻, or OH⁻.

Especially preferred are phenol sulfonate leaving groups. A preferredsynthesis of phenol sulfonate esters which could be adapted for useherein is disclosed in pending application Ser. No. 915,133, filed Oct.3, 1986, now Alfred G. Zielske, U.S. Pat. No. 4,735,740, commonlyassigned to The Chlorox Company, said application being incorporatedherein by reference.

Non-limiting preferred phenol derivatives are: ##STR24##

The halide leaving groups are quite reactive and actually are directlyobtained as the intermediates in the synthesis of the phenyl sulfonateand t-butylphenol esters. While halides include Br and F. C₁ is mostpreferred. A non-limiting example is:

--Cl (Chloride)

(c) Oxynitrogen

The oxynitrogen leaving groups are especially preferred. In theco-pending application entitled "Acyloxynitrogen Peracid Precursors,"inventor Alfred G. Zielske, commonly assigned to The Clorox Company,Oakland, Calif. filed concurrently herewith, Ser. No. 928,065, filedNov. 6, 1986 incorporated herein by reference, a detailed description ofthe synthesis of these leaving groups is disclosed. These oxynitrogenleaving groups are generally disclosed as --ONR⁶, wherein R⁶ comprisesat least one carbon which is singly or doubly bonded directly to N.--ONR⁶ is more specifically defined as: ##STR25##

Oxime leaving groups have the structure ##STR26## wherein R⁷ and R₈ areindividually H, C₁₋₂₀ alkyl, (which can be cycloalkyl, straight orbranched chain), aryl, or alkylaryl and at least one of R⁷ and R⁸ is notH. Preferably R⁷ and R⁸ are the same or different, and range from C₁₋₆.Oximes are generally derived from the reaction of hydroxylamine witheither aldehydes or ketones.

Non-limiting examples of an oxime leaving group are: (a) oximes ofaldehydes (aldoximes), e.g., acetaldoxime, benzaldoxime,propionaldoxime, butylaldoxime, heptaldoxime, hexaldoxime,phenylacetaldoxime, p-tolualdoxime, anisaldoxime, caproaldoxime,valeraldoxime and p-nitrobenzaldoxime; and (b) oximes of ketaones(ketoximes), e.g., acetone oxime (2-propanone oxime), methyl ethylketoxime (2-butanone oxime), 2-pentanone oxime, 2-hexanone oxime,3-hexanone oxime, cyclohexanone oxime, acetophenone oxime, benzophenoneoxime, and cyclopentanone oxime.

Particularly preferred oxime leaving groups are: ##STR27##

Hydroxyimide leaving groups comprise: ##STR28## wherein R⁹ and R¹⁰ canbe the same or different, and are preferably straight chain or branchedC₁₋₂₀ alkyl, aryl, alkylaryl or mixtures thereof. If alkyl, R⁹ and R¹⁰can be partially unsaturated. It is especially preferred that R⁹ and R¹⁰are straight or branched chain C₁₋₆ alkyls, which can be the same ordifferent. R¹¹ is preferably C₁₋₂₀ alkyl, aryl or alkylaryl, andcompletes a heterocycle. R¹¹ includes the preferred structure ##STR29##wherein R¹² can be an aromatic ring fused to the heterocycle, or C₁₋₆alkyl (which itself could be substituted with water solubilizing groups,such as EO, PO, CO₂ ⁻ and SO₃ ⁻).

These esters of imides can be prepared as described in Greene,Protective Groups in Organic Synthesis. p. 183, (incorporated byreference) and are generally the reaction products of acid chlorides andhydroxyimides.

Non-limiting examples of N-hydroxyimide which will provide thehydroxyimide leaving groups of the invention include:N-hydroxysuccinimide, N-hydroxyphthalimide, N-hydroxyglutarimide.N-hydroxynaphthalimide, N-hydroxymaleimide, N-hydroxydiacetylimide andN-hydroxydipropionylimide.

Especially preferred examples of hydroxyimide leaving groups are:##STR30##

In the first preferred structure for amine oxides, R¹³ and R¹⁴ can bethe same or different, and are preferably C₁₋₂₀ straight or branchedchain alkyl, aryl, alkylaryl or mixtures thereof. If alkyl, thesubstituent could be partially unsaturated. Preferably, R¹³ and R¹⁴ areC₁₋₄ alkyls and can be the same or different. R¹⁵ is preferably C₁₋₃₀alkyl, aryl, alkylaryl and mixtures thereof. This R¹⁵ substituent couldalso be partially unsaturated. It is most preferred that R¹³ and R¹⁴ arerelatively short chain alkyl groups (CH₃ or CH₂ CH₃) and R¹⁵ ispreferably C₁₋₂₀ alkyl, forming together a tertiary amine oxide.

Further, in the second preferred amine oxide structure, R¹⁶ can be C₁₋₂₀alkyl, aryl or alkylaryl, and completes a heterocycle. R¹⁶ preferablycompletes an aromatic heterocycle of 5 carbon atoms and can be C₁₋₆alkyl or aryl substituted. R¹⁷ is preferably nothing, C₁₋₃₀ alkyl, aryl,alkylaryl or mixtures thereof. R¹⁷ is more preferably C₁₋₂₀ alkyl if R¹l completes an aliphatic heterocycle. If R¹⁶ completes an aromaticheterocycle, R¹⁷ is nothing.

Non-limiting examples of amine oxides suitable for use as leaving groupsherein can be derived from: Pyridine N-oxide, trimethylamine N-oxide,4-phenyl pyridine N-oxide, decyldimethylamine N-oxide,dodecyldimethylamine N-oxide, tetradecyldimethylamine N-oxide,hexadecyldimethylamine N-oxide, octyldimethylamine N-oxide,di(decyl)methylamine N-oxide, di(dodecyl)methylamine N-oxide,di(tetradecyl)methylamine N-oxide, 4-picoline N-oxide, 3-picolineN-oxide and 2-picoline N-oxide.

Especially preferred amine oxide leaving groups include: ##STR31##

(d) Carboxylic Acids from Mixed Anhydrides

Carboxylic acid leaving groups have the structure ##STR32##

wherein R¹⁸ is C₁₋₁₀ alkyl, preferably C₁₋₄ alkyl, most preferablyeither CH₃ or CH₂ CH₃ and mixtures thereof.

When R¹⁸ is C₁ and above, it is believed that the leaving groups willform carboxylic acids upon perhydrolytic conditions. Thus, when R¹⁸ isCH₃, acetic acid would be the leaving group; when CH₂ CH₃, propionicacid would be the leaving group, and so on. However, the foregoingtheory is non-binding and offers only one explanation for what may be avery complicated reaction.

Non-limiting examples of mixed anhydride esters include: ##STR33##

A preferred synthesis of these mixed anhydrides appears in theEXPERIMENTAL section below.

The Peracid Alkanoyloxyperacetic Acid (I)

In another especially preferred embodiment of the invention. is provideda new organic peracid, which will be named alkanoyloxyperacetic acid(but, it R is aryl, the peracid is benzoyloxyperacetic acid; and, if Ris alkylaryl, the peracid is alkylbenzoyloxy peracetic acid), of thestructure. ##STR34##

wherein R is defined, as for the precursor, as C₁₋₂₀ linear or branchedalkyl, alkoxylated alkyl, cycloalkyl, aryl, alkylaryl, substituted aryland R' and R" are independently H, C₁₋₂₀ alkyl, aryl, C₁₋₂₀ alkylaryl,substituted aryl, and NR₃ ^(a+), wherein R^(a) is C₁₋₃₀ alkyl.

The peracid is generated in situ when the inventive precursor ##STR35##

is placed in aqueous solution with a source of hydrogen peroxide whichgives rise to perhydroxide anions.

The novel peracid could be synthesized separately, but, because it isfairly unstable--in fact, unless stabilized by exothermic control agentsor the like, it might be somewhat explosive -- it is best to generatethe compound in situ. This has the added advantage of freeing thesynthetic chemist from having to isolate the peracid, to purify it and,of course, to stabilize it.

The peracid is quite unique since, depending on pH (e.g., greater thanabout 10). the peracid will itself undergo secondary perhydrolysis togive rise to up to potentially two other peracids, namely, the peracidcorresponding to the moiety R (II) and perhydroxyacetic acid (III).##STR36##

Beneficially, since up to three different peracids potentially capableof attacking different substrates (stains) can be generated, theinventive peracid offers advantages over prior art peracids. Forexample, EP 68 547 calls for a mixture of separately synthesizedhydrophobic, hydrophilic and hydrotropic peracids for allegedly improvedtextile bleaching. The new peracid, alkanoyloxyperacetic acid will,under certain conditions, provide the three separate peracids from asingle compound. or C₁₋₂₀ alkyl, more preferably C4-17 alkyl, and mostpreferably C₆₋₁₂ alkyl. When R is alkyl between C₄₋₁₇, most preferablyC₆₋₁₂ alkyl, surface active peracids result, which would appear to havegreater oil--and grease based soil removal potential at lower washtemperatures.

Non-limiting examples include: ##STR37##

The above peracids can include other substituents, for instance, the Rgroup can be ethoxylated or propoxylated. Electronegative groups, suchas halide, can be added to the alkyl chain, or on the phenyl ring.

A singularly important embodiment of this novel peracid is to stabilizethe same, by neutralizing the peracid with either (preferably) analkaline earth or alkali metal hydroxide, to give rise to the alkalineearth and alkali metal salts of the peracid. respectively: ##STR38##where M' is an alkali metal or alkaline earth salt and m=1 or 2.

Non limiting examples of such alkali metals include monovalent cations,Na+, Li+and K+. Non-limiting alkaline earth metals would be divalentcations Ca++, Sr++and, most preferably. Mg++.

The Peracid Perglycolic Acid (III)

In yet another especially preferred embodiment of the invention, isprovided a new organic peracid, which will be named perglycolic acid orhydroxyperacetic acid. It has the structure: ##STR39##

The peracid is generated in situ when the inventive precursor ##STR40##is placed in aqueous solution with a source of hydrogen peroxide whichgives rise to perhydroxide anions, at a pH of greater than about 10.

This inventive peracid has the more general structure ##STR41##

In the above structure. R' and R" are the substituents previouslydefined, although, again, it is most preferred for R' and R" both to behydrogen.

The novel peracid could be synthesized separately, but, because it isfairly unstable--in fact, unless stabilized by exothermic control agentsor the like, it might be somewhat explosive--it is best to generate thecompound in situ. This has the added advantage of freeing the syntheticchemist from having to isolate the peracid, to purify it and, of course,to stabilize it.

The peracid is quite unique since, depending on pH (e.g.. greater thanabout 10). it is a product of the secondary perhydrolysis of the othernovel peracid, alkanoyloxyperacetic acid, as described above on page 22,lines 1.5. As in the case of the other novel peracid, it may bedesirable to obtain the alkali metal or alkaline earth salt ofhydroxyperacetic acid in order to stabilize the same. The same salts asdescribed for the prior, novel peracid would be applicable. ##STR42##

In yet one more preferred embodiment of the invention, is provided

a bleaching composition comprising:

(a) a compound with the structure ##STR43## (b) a bleach effectiveamount of a source of hydrogen peroxide, wherein R is, as previouslydefined, as C₁₋₂₀ linear or branched alkyl, alkoxylated alkyl,cycloalkyl, aryl, alkylaryl, substituted aryl, and R' and R" areindependently H. C₁₋₂₀ alkyl, aryl. C₁₋₂₀ alkylaryl, substituted aryl,and NRa+, wherein R^(a) is C₁₋₃₀ alkyl;

said composition providing about 0.5 to 100 ppm A.0. in aqueous media.

in the above structure completes an alkoxy ester.

R¹⁹ is

The alkoxy groups have the structures --O--R¹⁹. R¹⁹ is preferably C₁₋₂₀alkyl, although the same criteria for the R of the acyl group apply. R¹⁹is especially preferred as C₁₋₁₀, for example, preferably wherein R¹⁹forms the methyl, ethyl, propyl and butyl esters of alkanoyloxyaceticacid. Non-limiting examples of these alkoxy groups are:

--O--CH₃ (methyl ester)

--O--CH₂ CH₃ (ethyl ester)

--O--CH₂ CH₂ CH₃ (n-propyl ester)

In order to enhance the solubility of these compounds, it is preferredto add hydroxyl (--OH) groups to the alkoxy substituent, --R¹⁹. Thus,preferred alkoxy esters would be polyhydroxylated. ##STR44##

In still one further especially preferred embodiment of the invention isprovided:

a bleaching composition comprising:

(a) a compound which includes the substituent ##STR45## (b) a bleacheffective amount of a source of hydrogen peroxide, wherein R is, aspreviously defined, as C₁₋₂₀ linear or branched alkyl, alkoxylatedalkyl, cycloalkyl, aryl, alkylaryl, substituted aryl and n is an integerfrom 1 to 6. most preferably 1 to 3;

said composition providing about 0.5 to 100 ppm A. O. in aqueous media.##STR46## (when R' and R" are both hydrogen) will be present in a numberof different compounds and the only real proviso for excluding anycompound from this definition would be that the particular compound doesnot generate peracid A.O. in aqueous media. All of the disclosedprecursors and peracids herein would fit the definition of thiscomposition of matter.

Delivery Systems

The precursors can be incorporated into a liquid or solid matrix for usein liquid or solid detergent bleaches by dissolving into an appropriatesolvent or surfactant or by dispersing onto a substrate material, suchas an inert salt (e.g, NaCl, Na₂ SO₄) or other solid substrate, such aszeolites, sodium borate, or molecular sieves. Examples of appropriatesolvents include acetone, non-nucleophilic alcohols, ethers orhydrocarbons. Other more water-dispersible or-miscible solvents may beconsidered. As an example of affixation to a substrate material, theprecursors of the present invention could be incorporated onto anon-particulate substrate such as disclosed in published European PatentApplication EP No. 98 129. whose disclosure is incorporated herein byreference.

While it has been disclosed by applicants that substituting solubilizinggroups may improve the solubility and enhance the reactivity of theseprecursors, an alternate mode and preferred embodiment is to combine theprecursors with a surfactant.

For example, the inventive precursors with oxynitrogen leaving groupsare apparently not as soluble in aqueous media as compared to phenylsulfonates. Other precursors may be similarly somewhat less soluble thanphenyl sulfonate esters. Thus, a preferred embodiment of the inventionis to combine the precursors with a surfactant. It is particularlypreferred to coat these precursors with a nonionic or anionic surfactantthat is solid at room temperature and melts at above about 40° C. A meltof surfactant may be simply admixed with peracid precursor, cooled andchopped into granules. Exemplary surfactants for such use areillustrated in Table IV below:

                  TABLE IV                                                        ______________________________________                                        Commercial Name                                                                            m.p.     Type      Supplier                                      ______________________________________                                        Pluronic F-98                                                                              55° C.                                                                          Nonionic  BASF Wyandotte                                Neodol 25-30 47° C.                                                                          Nonionic  Shell Chemical                                Neodol 25-60 53° C.                                                                          Nonionic  Shell Chemical                                Tergitol-S-30                                                                              41° C.                                                                          Nonionic  Union Carbide                                 Tergitol-S-40                                                                              45° C.                                                                          Nonionic  Union Carbide                                 Pluronic 10R8                                                                              46° C.                                                                          Nonionic  BASF Wyandotte                                Pluronic 17R8                                                                              53° C.                                                                          Nonionic  BASF Wyandotte                                Tetronic 90R8                                                                              47° C.                                                                          Nonionic  BASF Wyandotte                                Amidox C5    55° C.                                                                          Nonionic  Stepan                                        ______________________________________                                    

The precursors, whether coated with the surfactants with meltingcompletion temperatures above about 40° C. or not so coated, could alsobe admixed with other surfactants to provide, depending on formulation,either bleach additive or detergent compositions.

Particularly effective surfactants appear to be nonionic surfactants.Preferred surfactants of use include linear ethoxylated alcohols, suchas those sold by Shell Chemical Company under the brand name Neodol.Other suitable nonionic surfactants can include other linear ethoxylatedalcohols with an average length of 6 to 16 carbon atoms and averagingabout 2 to 20 moles of ethylene oxide per mole of alcohol; linear andbranched, primary and secondary ethoxylated, propoxylated alcohols withan average length of about 6 to 16 carbon atoms and averaging 0-10 molesof ethylene oxide and about 1 to 10 moles of propylene oxide per mole ofalcohol; linear and branched alkylphenoxy (polyethoxy) alcohols,otherwise known as ethoxylate alkylphenols, with an average chain lengthof 8 to 16 carbon atoms and averaging 1.5 to 0 moles of ethylene oxideper mole of alcohol; and mixtures thereof. Further suitable nonionicsurfactants may include polyoxyethylene carboxylic acid esters, fattyacid glycerol esters, fatty acid and ethoxylated fatty acidalkanolamides, certain block copolymers of propylene oxide and ethyleneoxide, and block polymers of propylene oxide and ethylene oxide withpropoxylated ethylene diamine. Also included are such semi-polarnonionic surfactants like amine oxides, phosphine oxides, sulfoxides,and their ethoxylated derivatives.

Anionic surfactants may also be suitable. Examples of such anionicsurfactants may include the ammonium, substituted ammonium (e.g.,mono-di-, and triethanolammonium). alkali metal and alkaline earth metalsalts of C₆ -C₂₀ fatty acids and rosin acids, linear and branched alkylbenzene sulfonates, alkyl sulfates, alkyl ether sulfates, alkanesulfonates, olefin sulfonates, hydroxyalkane sulfonates, fatty acidmonoglyceride sulfates, alkyl glyceryl ether sulfates, acyl sarcosinatesand acyl N-methyltaurides.

Suitable cationic surfactants may include the quaternary ammoniumcompounds in which typically one of the groups linked to the nitrogenatom is a C₁₂ -C₁₈ alkyl group and the other three groups are shortchained alkyl groups which may bear inert substituents such as phenylgroups.

Further, suitable amphoteric and zwitterionic surfactants which containan anionic water-solubilizing group, a cationic group and a hydrophobicorganic group may include amino carboxylic acids and their salts, aminodicarboxylic acids and their salts, alkylbetaines, alkylaminopropylbetaines, sulfobetaines, alkyl imidazolinium derivativescertain quaternary ammonium compounds, certain quaternary phosphoniumcompounds and certain tertiary sulfonium compounds. Other examples ofpotentially suitable zwitterionic surfactants can be found described inJones, U.S. 4,005,029, at columns 11-15, which are incorporated hereinby reference.

Further examples of anionic, nonionic, cationic and amphotericsurfactants which may be suitable for use in this invention are depictedin Kirk Othmer, Encyclopedia of Chemical Technology, Third Edition,Volume 22, pages 347-387, and McCutcheon's Detergents and Emulsifiers,North American Edition, 1983, which are incorporated herein byreference.

As mentioned hereinabove, other common detergent adjuncts may be addedif a bleach or detergent bleach product is desired. If, for example, adry bleach composition is desired, the following ranges (weight %)appear practicable:

    ______________________________________                                        0.5-50.0%      Hydrogen Peroxide Source                                       0.05-25.0%     Precursor                                                      1.0-50.0%      Surfactant                                                     1.0-50.0%      Buffer                                                         5.0-99.9%      Filler, stabilizers, dyes,                                                    Fragrances, brighteners, etc.                                  ______________________________________                                    

The hydrogen peroxide source may be selected from the alkali metal saltsof percarbonate, perborate, persilicate and hydrogen peroxide adductsand hydrogen peroxide. Most preferred are sodium percarbonate, sodiumperborate mono-and tetrahydrate, and hydrogen peroxide. Other peroxygensources may be possible, such as monopersulfates and monoperphosphates.In liquid applications, liquid hydrogen peroxide solutions arepreferred, but the precursor may need to be kept separate therefromprior to combination in aqueous solution to prevent prematuredecomposition.

The range of peroxide to peracid precursor is preferably determined as amolar ratio of peroxide to precursor. Thus, the range of peroxide toeach precursor is a molar ratio of from about 0.5 to 10:1. morepreferably about 1:1 to 5:1 and most preferably about 1:1 to 2:1. It ispreferred that this peracid precursor/peroxide composition providepreferably about 0.5 to 100 ppm A.O. and most preferably about 1 to 50ppm A.O. and most preferably

A description of, and explanation of, A.O. measurement is found in thearticle of Sheldon N. Lewis. "Peracid and Peroxide Oxidations," In:Oxidation. 1969, pp. 213-258, which are incorporated herein byreference. Determination of the peracid can be ascertained by theanalytical techniques taught in Organic Peracids. (Ed. by D. Swern),Vol. 1. pp. 501 et sec. (Ch.7) (1970), incorporated here by reference.

An example of a practical execution of a liquid delivery system is todispense separately metered amounts of the precursor (in somenon-reactive fluid medium) and liquid hydrogen peroxide in a containersuch as described in Beacham et al, U.S. Pat. No. 4,585.150. commonlyassigned to The Clorox Company, and incorporated herein by reference.

The buffer may be selected from sodium carbonate, sodium bicarbonate,sodium borate, sodium silicate. Phosphoric acid salts, and other alkalimetal/alkaline earth metal salts known to those skilled in the art.Organic buffers, such as succinates, maleates and acetates may also besuitable for use. It appears preferable to have sufficient buffer toattain an alkaline pH. i.e., above at least about 7.0. Also, as furtherdiscussed below, it is especially advantageous to have an amount ofbuffer sufficient to maintain a pH of about 10.5.

The filler material, which, in a detergent bleach application, mayactually constitute the major constituent, by weight, of the detergentbleach, is usually sodium sulfate. Sodium chloride is another potentialfiller. Dyes include anthraquinone and similar blue dyes. Pigments, suchas ultramarine blue (UMB), may also be used, and can have a bluingeffect by depositing on fabrics washed with a detergent bleachcontaining UMB. Monastral colorants are also possible for inclusion.Brighteners, such as stilbene, styrene and styrylnapthalene brighteners(fluorescent whitening agents), may be included. Fragrances used foresthetic purposes are commercially available from Norda, InternationalFlavors and Fragrances and Givaudon. Stabilizers include hydrated salts,such as magnesium sulfate, and boric acid.

In one of the preferred embodiments in which a glycolate ester compoundsuch as in Example III below is the precursor, a preferred bleachcomposition has the following ingredients:

    ______________________________________                                        15.6%          Sodium Perborate Tetrahydrate                                  19.0%          Octanoyl glycolate, p-phenyl sulfonate                         7.0%           Nonionic Surfactant                                            15.0%          Sodium Carbonate                                               43.4%          Sodium Sulfate                                                 100.0%                                                                        ______________________________________                                    

In another one of the preferred embodiments, in which another glycolateester compound such as in Example VIII below is the precursor, apreferred bleach composition has the following ingredients:

    ______________________________________                                        15.5%         Sodium Perborate Tetrahydrate                                   16.8%         Octanoyloxy acetic acid, t-butyl phenol ester                   7.0%          Nonionic Surfactant                                             15.0%         Sodium Carbonate                                                45.7%         Sodium Sulfate                                                  100.0%                                                                        ______________________________________                                    

Other peroxygen sources, such as sodium perborate monohydrate or sodiumpercarbonate are suitable. If a more detergent-type product is desired,the amount of filler can be increased and the precursor halved orfurther decreased.

The EXPERIMENTAL section follows hereto. Examples I through XVI depictin detail the syntheses of various inventive precursors. Example XVIIdemonstrates the excellent perhydrolysis of these inventive precursors.

EXPERIMENTAL

In Examples I through III and IV through VI, the following synthesisroute for the synthesis of p-phenylsulfonate esters of alkanoyloxyaceticacid is followed: ##STR47##

EXAMPLE I Synthesis of Octanoyloxyacetic acid preparation ##STR48##

Procedure: A 1 liter, 2 neck round bottom flask was charged with 110.7g(1.46 moles) glycolic acid (Kodak, 97%), 294 g (2.91 moles)triethylamine (TEA, Aldrich 99%), 2.0 g 4-dimethylamino dine (DMAP, 0.16mole) and 200 ml CHCl₃. Dissolution was obtained by mechanical stirringwhile cooling to 3°-4° C. on an ice water bath (an exothermic reactionoccurred upon mixing). 0.237g (1.46 mole) octanoyl chloride (Aldrich99%) was added dropwise via additional funnel over one- and one halfhours, during which time a heavy precipitate (triethylaminehydrochloride) formed. The reaction was stirred an additional one-andone half hours. The solids were filtered off (wt. approx. 190 g); andthe supernatant (CHCl₃) was washed with: 2×500 ml 6% (aq) HCl, 1×500 mlwater, and 1×500 ml saturated NaC₁ (aq). The chloroform layer was driedover MgSO₄, filtered and rotary evaporated to an oil (extract I) (wt=248g).

The filtered triethylamine hydrochloride was extracted with 500 mldiethyl ether, which in turn was washed with 250ml 6% MCl, and 250 mlsaturated NaCl, dried over MgSO₄, filtered and rotary evaporated to anoil (Extract II).

Extracted oils I and II were combined and recrystallized from mlpetroleum ether (-20° C.). The crystalline product was isolated byfiltration and dried in vacuo. (wt.=130 g) (mp 44-46° C.; approximate %purity, 90 %; Isolated yield=40 %.

The ¹³ C-NMR (CDCl₃, ppm downfield from TMS) showed only absorptionsexpected for the product. Using the numbering system shown, theseassignments were made: ##STR49## C₁ (13.7), C₂ (22.3), C₃ (24.5), C₄(28.7), C₅ (31.4), C₆ (33.4), C₇ (173.1), C₈ (59.9), and C₉ (173).

EXAMPLE II Synthesis of Octanoyloxy acetyl chloride ##STR50##

Procedure: 101.1 g (0.5 mole) octanoyloxyacetic acid and 83 g (0.65mole) oxalyl chloride are combined in a 1 liter round bottom flask witha magnetic stir bar and a CaSO₄ drying tube (note: a little hexane orpetroleum ether can be added if the solid does not completely dissolve).The reaction is stirred at room temperature while rapid gas evolution isnoted, then gradually heated to 40-50° C. for 1 hour (note: the reactioncan also be run at room temperature overnight with the advantage that itremains colorless). The slightly yellow solution is then heated to60-70° C. under aspirator pressure for 1 to 11/2 hours to remove excessoxalyl chloride. After cooling to room temperature the oil is dilutedwith 400 ml petroleum ether (bp 30-60° C.) and extracted with 3×200 mlice water (caution: gas evolution can be vigorous). The organic layer isdried over MgSO₄, filtered and rotovapped to a clear straw colored oil,weight= 11.57 g (111.4 g theoretical). IR showed no acid--OH stretch andtwo carbonyls at 1812 cm⁻¹ and at 1755 cm⁻¹.

EXAMPLE III

Synthesis of Octanoyloxy acetic acid, phenyl sulfonate ester ##STR51##

Procedure: 17.3 g (0.079 mole) octanoyloxyacetyl chloride and 17.0 g(0.087 mole) sodium phenol sulfonate (dried at 120° C. in vacuo for 16hours) were combined in a 250 ml round bottom flask with a magnetic stirbar. 30 ml of ethylene glycol-dimethyl ether (glyme) was added, and theslurry stirred with cooling in an ice-water bath. 7.8 g (0.077 mole)triethyl amine was placed in an addition funnel equipped with a CaSO₄drying tube and this was added dropwise to the above slurry over 1/2hour becomes very thick during this time and more glyme (or ethyl ether)can be added at this time to allow efficient stirring. The reaction wasstirred for two hours at room temperature, diluted with ethyl ether andstirred 1 hour more. The reaction was filtered on a coarse frittedfunnel washed with several portions of ethyl ether, suction-dried for 1hour and then dried in vacuo at room temperature.

Weight of product: 39g (theoretical wt 42.1 g). This material can berecrystallized from 60/40 (vol/vol) isopropanol/water in an approximate3 to 4:1 (wt/wt) ratio of solvent to ester reaction mixture to give anapproximate 45-60% yield of ester (95 % in purity).

The ¹³ C-NMR (D₂ O, ppm downfield from TMS) showed only absorptionsexpected for the product. Using the numbering system shown, theseassignments were made: ##STR52## C₁ (15.9), C₂ (24.7), C₃ (27.0), C₄(31.0/31.2), C₅ (33.9), C₆ (35.9), C₇ (175.9), C₈ (63.3), C₉ (169.7),C₁₀ (153.9), C₁₁ (123.8), C₁₂ (130.0) and C₁₃ (144.4).

EXAMPLE IV Synthesis of Hexanoyloxyacetic Acid ##STR53##

25.0 g (0.329 m) of glycolic acid (m.pt. 78-80° C.) 66 g (0.66 m) oftriethylamine, and 2.0 g (0.016m) of 4-dimethylaminopyridine weredissolved in 200 ml chloroform in a one liter round bottom flask fittedwith a mechanical stirrer and an addition funnel. The solution wascooled to about 5° C. with an ice water bath, and 45.6g (0.329 m) ofn-hexanoyl chloride was added dropwise via the addition funnel over onehour. The resulting slurry was stirred

for two hours at 0-5° C. after which time the salts were filtered offand the filtrate washed with 1×200 ml of 10%HCl and 1×200 ml saturatedsodium chloride. The organic phase was dried over 50 g Na₂ SO₄,filtered, and the CHCl₃ solvent removed via rotary vacuum evaporation. Alight yellow oil was obtained (46g, 80% yield).

The ¹³ C--NMR showed only those absorptions necessary for the product.An ester carbonyl at 173.2 (D₂ O solvent, ppm downfield from TMS) wasobserved, and a second carbonyl at 172.9, in addition to absorptions forthe methylene group of glycolic acid a 59.9ppm and those for the alkylchain.

EXAMPLE V Synthesis of Hexanoylacetyl Chloride ##STR54##

8.7g (0.05 m) of hexanoylacetic acid and 12.7 g (0.10m) of oxalylchloride were mixed together at room temperature. The reaction washeated gradually over one hour to 50-60° C., then to 60-70° C. underaspirator pressure for one hour. The reaction mixture was diluted with125 ml hexane, washed with 3×100 ml ice water, dried over 20 g MgSO₄,and roto-vapped at 50° C. to yield an oil (9.4 g, 98% yield).

EXAMPLE VI Synthesis of Sodium, n-Hexanoyloxyacetate, p-phenylsulfonate##STR55##

9.2 g (0.04 m) of n-hexanoyloxyacetyl chloride was added dropwise to anice-cooled slurry of 9.0 g (0.046 m) sodium, p-phenolsulfonate (driedfour hours at 110° C. in vacuo) and 5.5 g (0.045 m) triethylamine in 45ml diglyme in a 100 ml round bottom flask fitted with a stirrer and lowtemperature thermometer. The reaction mixture was stirred for two hoursat 0-4° C., diluted with 100 ml ethyl ether, and filtered. The whitesolid precipitate was triturated with 100 ml of warm isopropanol and thesolid was vacuum filtered and dried overnight under house vacuum (11.5g, 65% yield). The ¹³ C-NMR showed only those absorptions necessary forthe An ester carbonyl at 175.9 (D₂ O solvent, ppm downfield from TMS)was observed, and the terminal carbonyl at 169.7, in addition to thoseabsorptions for the aromatic carbons and those the alkyl chain.

EXAMPLE VII Synthesis of Octanoyloxyacetate, dimethyl oxime ester##STR56##

After obtaining the acid chloride of Example II, the oxime ester thereofwas synthesized by following the procedure of Example I, in theco-pending application Ser. No. 928,065 (which is incorporated in itsentirety herein by reference) entitled "Acyloxynitrogen PeracidPrecursors," inventor Alfred G. Zielske, filed Nov. 6, 1986 same date,commonly assigned to The Clorox Company. The ¹³ C--NMR showed only thoseabsorptions necessary for the product. An ester carbonyl at 171 (CDCl₃solvent, ppm downfield from TMS) was observed, and the terminal carbonylat 164.6, in addition to the absorption for the oxyimide group and thealkyl chain.

EXAMPLE VIII Synthesis of Octanoyloxyacetate, t-butyl phenol ester##STR57##

5.95 g (0.025 m) octanoyloxyacetyl chloride (which can be prepared fromthe steps in Examples I and II above) dissolved in about 15 ml anhydrousethyl ether are added drop wise to a solution containing 21/2]g (0.027m) pyridine and 4.70 g (0.031 m) t-butyl phenol in about 100 ml pyridineover one half hour the solution being maintained at a temperature of0-4° C. in an ice bath and stirred via a magnetic stir bar. The reactionwas stirred at 5-10° C. for about 2 hours, filtered and then diluted toabout 200 ml with ethanol. This was washed with 3 parts of 100 ml of 4 %hydrochloric acid, one part of 150 ml water, two parts of 100ml of 10%sodium carbonate solution, then dried over sodium sulfate. The productwas filtered and roto-vapped to yield a yellow oil. This waschromatographed on 60 g of silica gel with 4 % ethyl ether/petroleumether distillate. The resulting product was 5.3 g of a yellow oil (8.83g theoretical), for about 60% product yield. Product purity wasdetermined to be about 99.9%±0.5%. IR spectroscopy show no peaks about3000 cm³¹, and two carbonyls at 1785⁻¹ cm and 1750⁻¹ cm, respectively.

The ¹³ C--NMR showed only those absorptions necessary for the product.An ester carbonyl at 173.0 (CDCl₃ solvent, ppm downfield from TMS) wasobserved, and the terminal carbonyl at 166.6, in addition to thoseabsorptions for the aromatic carbons and those for the alkyl chain.

The ¹³ C--NMR (CDCl₃, ppm downfield from TMS) showed only absorptionsexpected for the product. Using the numbering system shown, theseassignments were made: ##STR58## C₁(14 0), C₂ (22.6), C₃ (24.9), C₄(29.0), C₅ (31.6), C₆ (33 8), C₇ (173.0), C₈ (60 5), C₉ (166.6), C₁₀(148.9), C₁ (126.3), C₁₂ (120.6), C₁₃ (147.9), C₁₄ (34.5) and C₁₅(31,4).

Perhydrolysis yield of the ester (at 8.75×10⁻⁴ M) with hydrogen peroxide(1.75 x 10-3M) at pH 10.5 (0.02M NaHCO₃ / NaOH hardness) at 21° C. was80% A.O. in 10 minutes.

EXAMPLE X Alternate Synthesis of Acyloxvacetic Acid (acylolycolic acid)##STR59##

Following the synthesis described in Wayo, U.S. Pat. No. 2,659,697,acyloxyacetic acid (acylglycolic acid) can be synthesized by combining aneutralized carboxylic acid with chloroacetic acid.

EXAMPLE XI Synthesis of Alkyl Esters of Acyloxyacetic Acid ##STR60##

Alkyl esters of acyloxyacetic acid can be prepared in accordance withthe method described in Loder et al, U.S. Pat. No. 2,350,964 or Burtonand Fife, "Preparation of a Series of Carbethoxymethyl Alkanoates," J.Amer. Chem. Soc., vol. 74, pp 3935-6 (1952), both incorporated herein byreference, in which sodium salts of fatty acids are combined with sodiumacetate and a chloroacetate. Alternatively, the acid chloride synthesisdescribed in Examples I-III, IV-VI, above, may be followed, but alkoxysubstituents will be introduced via alcohol instead of phenyl sulfonate.

EXAMPLE XIII Benzoyl Oxyacetic Acid ##STR61##

(1) Salt Formation

(a) Lithium Chloroacetate: 9.45 g (0.10 m) chloroacetic acid wasdissolved in 30 ml methanol. 4.2 g lithium hydroxide (0.10 m) wasdissolved in 50 ml of methanol. The two methanol solutions were combinedand rotary evaporated to a white powder (wt=13 g).

(b) Lithium Benzoate: 25.6 g (0.21 m) benzoic acid was dissolved in 25ml methanol. 8.4 g (0.20 m) lithium hydroxide was dissolved in 75 mlmethanol. The two methanol solutions were combined and rotary evaporatedto a white powder. wt=31 g.

(2) Benzoyloxy Acetic Acid

13 g lithium chloroacetate (0.10 m) and 17.6 g lithium benzoate (0.10 m)were combined in a 250 ml R.b. flask with 50 ml DMF. This was heated onan oil bath to 110°-120° C. with magnetic stirring for 3 hrs. (Thesolution at first was clear, but after 2-3 hrs. a white precipitateformed).

The reaction was cooled to 100° C. and solvent distilled off under highvacuum, leaving a pasty residue which was dissolved in 150 of 4% HCl,which was extracted three times with 100 ml ethyl ether. The combinedether layer was dried over Na₂ SO₄, filtered and rotary evaporated to apaste weighing 14 g.

The product paste was chromatographed on 125 g silica gel in 33% ethylether/66% petroleum ether. Two cuts were made: Fraction I (1st 600 ml)which was impure product and Fraction II (next 400 ml) which contained2.2 g of one spot material as product. Fraction I (13 g) wasrechromatographed on 124 g silica gel (25/75 ethyl ether/pet. ether). 10Fifty ml fractions were taken. Fractions 6 through 10 continued 3.2 g ofpure product. Combined product 5.4 g (30% yield) (mp=107° C.).

The ¹³ C--NMR (D₂ O, ppm downfield from TMS) showed only absorptionsexpected for the product. Using the numbering system shown, theseassignments were made: ##STR62## C₁(173.1), C₂ (60.7), C₃ (166.1), C₄(129.1), C₅ (130), C₆ (128 5), and C₇ (133.5).

EXAMPLE XIV Benzoyl oxyacetate, Phenol Sulfonate Ester ##STR63##

(1) Benzoyloxyacetyl chloride

4.1 g (0.023 m) Benzoyloxy acetic acid (as synthesized in Example XIII)was combined with 2.96 ml (4.3 g, 0.032 m) oxalyl chloride in 50 mlpetroleum ether. This was stirred under a CaSO₄ drying tube for 5 hrs.,at which time 2.0 ml more oxalyl chloride and 50 ml chloroform wereadded. The reaction was stirred overnight.

Excess oxalyl chloride was removed at aspirator pressure by heating to55° C. on an oil bath. The reaction was diluted with ml hexane (a whiteprecipitate formed which was filtered off). The hexane layer was washedwith 5×50 ml ice cold H₂ O. The hexane layer was dried over 30 g Na₆SO₄, filtered and rotary evaporated to an oil wt=4.0 g (4.6 gtheoretical) (IR: one carbonyl at 18/5 cm⁻¹, another at 1740 cm⁻¹). Theoil was used as in in reaction (2), below.

(2) Benzoyloxy Acetic Acid, Phenol Sulfonate Ester

The 4.0 g (0.020 m) of acid chloride from (1) above was combined in a250 ml R.b. flask with 4.9 g 0.025 m) dried phenol sulfonate and 30 mlglyme. This slurry was stirred on an ice-water bath with a magnetic stirbar and 3.5 ml (2.5 g, 0.025 m) triethylamine (TEA) was added dropwise.Over the TEA addition the reaction thickened and turned yellow. Thereaction was stirred overnight following the addition of 30 ml glyme.

50 ml ethyl ether was added with stirring and the reaction was filteredon a C-Frit. The filter was washed with 2×40 ml ethyl ether. The crudeproduct filtrate was re-crystallized from 30 ml boiling IPA (70%vol)/water (30% vol). Cooling, filtration and vacuum drying (3hrs, 70°C.) gave 2.8 g of white powder, which was determined to be 78% productby HPLC, saponification, and NMR (¹³ C)

¹³ C--NMR confirms the desired product, phenol sulfonate and benzyl oxyacetic acid. Qualitative HPLC observes four peaks under the conditionsof analysis described. The purity value calculated from ester contentassumes that all ester groups are from the desired compound.

The ¹³ C--NMR (D₂ O, ppm downfield from TMS) showed only absorptionsexpected for the product. Using the numbering system shown, theseassignments were made: ##STR64## C₁(¹³⁶ 5), C₂ (¹³¹.3), C₃ (¹³².3), C₄ (¹³⁰.1), C₆ (64 0), C₇ (170.1), C₈ (154.1), C₉ (124.3), C₁₀ (¹³⁰.3), andC₁ (144 1).

EXAMPLE XV Octanoyloxy Acetic/Acetic Acid Mixed Anhydride ##STR65##

Procedure: One equivalent of octanoyloxy acetic acid (OOAA) and oneequivalent of pyridine are charged into a reaction vessel with THF(enough to keep the reaction fluid over its course). The mechanicallystirred reaction is begun on the slow dropwise addition of oneequivalent of acetyl chloride and stirring for approximately 1 hr. afteraddition. The pyridine hydrochloride is isolated by filtration and thesolvent removed on a rotary evaporator at low (30-35° C.) temperatureleaving behind the mixed anydride, yield should be nearly quantitative.

EXAMPLE XVI In Situ Generation of Octanoyloxyperacetic Acid ##STR66##

Octanoyloxy acetic acid, phenyl sulfonate ester (also known asoctanoylgycolate, phenyl sulfonate ester), as synthesized in the mannerof Example III, above, was treated with perhydroxide anion and highperformance liquid chromatography ("HPLC") was used to determine thepresence of the thus generated peracids, using an electrochemicaldetector which detects only peracids.

In the EC chromatogram, perglycolic acid (III) came off first at 1.55minutes, then peroctanoic acid (II) at 10.88 minutes and finally,octanoyloxyperacetic acid (peroctanoyloxyglycolic acid) (I) at 17.03minutes. In this assay, the following observed concentrations weremeasured: about 0.86 mM perglycolic acid, about 0.86 mM peroctanoicacid, and about 2.45 mM octanoyloxyglycolic acid. UV chromatogramascertained the presence of about 0.6 mM octanoic acid and about 1.69 mMoctanoyloxyacetic acid. About 4.0 mM total A.O. and about 4.17 mMperacid were found.

EXAMPLE XVII

The acyloxyacetic acid esters give excellent stain removal performance.Their performance is comparable to that of fatty acid based peracidswhich have been reported in the patent literature to be very efficientsurface active bleaching agents. TABLE V below discloses the crystalviolet stain removal data for the inventive precursors.

                  TABLE V                                                         ______________________________________                                                                 % SR(E)                                                                       Crystal                                              Compound                 Violet                                               ______________________________________                                        H.sub.2 O.sub.2          35                                                    ##STR67##               89                                                    ##STR68##               85                                                    ##STR69##               86                                                    ##STR70##               69                                                    ##STR71##               80                                                    ##STR72##               49                                                   ______________________________________                                         *pH 10.5, 5 min, 70° F., 2:1 molar ratio peroxide: activator,          Pluronic L63 surfactant (.1 wt %)                                        

What is claimed is:
 1. A peracid of the structure ##STR73## wherein R isC₁₋₂₀ linear or branched alkyl, alkoxylated alkyl, cycloalkyl, aryl,alkyl substituted aryl; and R' and R" are independently H, C₁₋₂₀ alkyl,aryl, C₁₋₂₀ alkyl, aryl, C₁₋₂₀ alkylaryl, aryl substituted with OH, CO₂or SO₃, and NR^(a+) ₃, wherein R^(a) is C₁₋₃₀ alkyl.
 2. The peracid ofclaim 1 wherein R is C₁₋₂₀ alkyl or aryl.
 3. The peracid of claim 2having the structure ##STR74## wherein R is C₄₋₁₇ alkyl, or aryl.
 4. Theperacid of claim 3 which is octanoyloxyperacetic acid.
 5. The peracid ofclaim 3 which is benzoyloxyperacetic acid.
 6. The alkali metal andalkaline earth salts of the peracid of claim
 1. 7. A peracid precursorof the structure ##STR75## wherein R is a C₁₋₂₀ straight or branchedchain, alkyl, alkoxylated alkyl, cycloalkyl, aryl, or alkyl substitutedaryl, R' and R" are independently H, C₁₋₂₀ alkyl, aryl, C₁₋₂₀ alkylaryl,aryl substituted with OH, SO₃ or CO₂, and NR₃ ^(a+), wherein R^(a) isC₁₋₃₀ alkyl, and L is a leaving group selected from: ##STR76## wherein Yand Z are individually H, SO₃ M, CO₂ M, SO₄ M, OH, halogen, --OR², R³,or NR₃ ⁴ X, wherein M is an alkali metal or alkaline earth metalcounterion, R² of --OR² is C₁₋₂₀ alkyl, R³ is C₁₋₆ alkyl, R⁴ of NR₃ ⁴ isC₁₋₃₀ alkyl, X is a counterpart ion, and Y and Z can be the same ordifferent;(b) --ONR⁶, wherein R⁶ comprises at least one carbon which issingly or doubly bonded directly to N; and (c) ##STR77## wherein R¹⁸ isC₁₋₁₀ alkyl.
 8. The precursor of claim 7 with the structure ##STR78## 9.The precursor of claim 7 with the structure ##STR79##
 10. The precursorof claim 7 with the structure ##STR80##
 11. The precursor of claim 7with the structure ##STR81## wherein R⁷ and R⁸ are each H or C₁₋₂₀alkyl, aryl, alkylaryl or mixtures thereof, and R⁷ and R⁸ can be thesame or different, but at least one of R⁷ or R⁸ is not H.
 12. Theprecursor of claim 7 with the structure ##STR82##
 13. The peracid ofclaim 3 which is heptanoyloxyperacetic acid.
 14. The peracid of claim 3which is nonanoyloxyperacetic acid.
 15. The peracid of claim 3 which isdecanoyloxyperacetic acid.
 16. The precursor of claim 8 which ishexanoyloxyacetyl phenyl sulfonate.
 17. The precursor of claim 8 whichis heptanoyloxyacetyl phenyl sulfonate.
 18. The precursor of claim 8which is octanoyloxyacetyl phenyl sulfonate.
 19. The precursor of claim8 which is nonanoyloxyacetyl phenyl sulfonate.
 20. The precursor ofclaim 8 which is decanoyloxyacetyl phenyl sulfonate.